Treatment of polymers



Aug. 5, 1958 R. A. FlNDLAY TREATMENT oF POLYMERS Filed March 14, 1957 INVENTOR. R.A. FlNDLAY A TTOIPNEKS` nite rates 'innert/inrit or roma/inns Robert A. Findlay, Bartlesville, lrla., assigner to Phillips Petroleum Company, a corporation of Delaware This invention relates to polymers and methods for their production. In one aspect, it relates to a method for producing polymers having a low ash content and a desirable color. ln another aspect, it relates to a method for treating polymer solutions so as to substantially reduce the ash content of the polymer.

The product obtained when producing olen polymers by catalytic polymerization often has a tan or brown color and/ or a high ash content. Various methods are described in the literature for overcoming one or both of these problems. For example, one method proposes washing the solid polymer with water, alcohol, acids or caustic solution in order to remove `bound metal portions of the catalyst. Such treatment may produce a white polymer, but it has been found that the yellow or tan color returns when the polymer is subjected to a molding or heating operation. Furthermore, this method of treatment fails to produce a polymer having a desirably low ash content.

Still other treating methods have been advanced but the same diiiculties as regards color and ash content are present. ln one method, the solid polymer is shaken with methanol, extracted with hydrochloric acid and then with acetone. Another method involves treating the solid polymer with dilute acids, e. g., l to l5 percent hydrochloric acid, with the addition of organic solvents, such as ether or alcohol. in still another method, the solid polymer is washed with methanol and then treated with dilute nitric acid at about D C. Polymers of undesirably high ash content are produced by each method, and the undesirable tan or yellow color reappears when the material is subjected to heat even though the material before such heating may be white.

For many uses, polymers of high ash content are very undesirable because the ash contributes, to poor electric properties, e. g., conductivity7 dielectric constant, dissipation factor, and the like. The reappearance of the tan or yellow color upon molding is, of course, obviously a very undesirable feature. For some applications, low ash content is of paramount importance while for other purposes the color is of primary significance. There are, of course, some uses which require both a snow white color and a Ilow ash content.

It is, therefore, an object of the present invention to provide an improved method of reducing the ash content of polymers wherein the color of the polymer, after being subjected to a molding operation, is greatly improved as compared to prior molded products.

Another object of the invention is to provide a method for treating polymer solutions in order to remove catalyst associated therewith.

A further object of the invention is to provide a system for treating solid polymers.

A still further object of the invention is to provide a process for polymerizing olens wherein catalyst recovered om a polymer solution is recycled to a polymerization zone, thereby resulting in improved productivity.

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Fatented Aug. 5, i958 Various other objects, advantages and features of the invention will become apparent to one skilled in the art upon consideration of the accompanying disclosure.

The instant invention resides in a process which eliminates or substantially minimizes the above-discussed problems with a resulting production of polymers of low ash content and/ or having a desired white color which is retained even after the polymer is subjected to a molding operation. Broadly speaking, the process comprises contacting a polymer in solution in a hydrocarbon solvent with a light hydrocarbon having a boiling point lower than that of the hydrocarbon solvent, and separately recovering a catalyst-rich phase and a polymer-rich phase. rthe treating operation is preferably carried out in a contacting tower, the upper portion of which is maintained at a higher temperature, e. g., 5() to 100 F. higher, than its lower portion. This treating operation results in a very substantial reduction in the ash content of the polymer. Furthermore, the polymer which is recovered from the polymer-rich phase has an improved color which is retained even when the polymer is subjected to a molding operation.

A more comprehensive understanding of the invention can fbe obtained by referring to the rdrawing which is a flow diagram illustrating a preferred embodiment of the invention. ln the description, the conditions are se forth which are suitable for the treatment of polyethylene in accordance with the invention. However, it will be understood that these conditions will vary somewhat depending upon the material treated, the nature of the catalyst used and other operating conditions. Such variations will be apparent to those skilled in the art.

Referring now to the drawing, a catalyst charge cornprising equal parts of triisobutylaluminum and titanium tetrachloride in cyclohexane is charged to reactor il? through lines M and l2. Although the cyclohexane and catalyst are shown as entering the reactor together, it is within the scope of the invention to introduce these materials separately into the reactor. Ethylene is introduced into the lower portion of the reactor Ml through line 13. The reactant materials are charge-d to the reactor at a rate Such as to provide a reactor eiluent stream containing about 6.0 percent by weight polyethylene, based on the total eiiuent. While the concentration of the polymer in the effluent can vary within rather wide limits, it should be maintained below 20 weight percent in order to prevent the effluent from becoming too viscous for subsequent treating. However, if the reactor emuent contains more than the desired concentration of polymer, it can be further `diluted by addition of cyclohexane prior to being treated by the process of this invention. With certain polymers, e. g., those having a relatively low molecular weight, a polymer concentration as high as 25 percent can be readily employed. The amount of catalyst charged is 1 percent by weight, lbased on the total reaction mixture. Although any amount of catalyst can be used which is sufficient to provide the desired polymeric product, the amount which is normally used is in the range of 0.91 to 5 weight percent or higher, based on the total reaction mixture.

Reactor lil is provided with a stirrer driven hy motor (not shown) in order to thoroughly7 agitare be contents of the reactor. The polymerization reactiis preferably conducted in the mixed phase, i. e., with the vessel only partially lled with liquid. Reactor lf3 is also provided with a heat exchange coil i6 through which a suitable heat exchange fluid is circulated in order to maintain a desired polymerization temperature within the reactor. While in this embodiment of the invention the polymerization temperature is about the temperature can vary over a broad range. For example,

the polymerization temperature can vary from about 250 F. to 500 F., with a temperature in the range of zero to 350 F. being usually employed. The pressure in the reactor is maintained at 250 p. s. i. g. While the pressure can vary over a wide range so long as the solvent is maintained in theliquid phase, pressures in the range of 30 to 500 p. s. i. g. are usually maintained.

Reactor effluent is withdrawn from the reactor through line 17 and then passed to flash chamber 18 which is maintained at a pressure somewhat lower, e. g., 25 to 50 p. s. i. g. lower, than the pressure in reactor l0. As a result of this lowering of the pressure in the flash chamber, unreacted ethylene contained in the reactor ellluent is `flashed ol and removed from the liash cham-y ber through line i9. The ethylene recovered through line 19 can be recycled to line 13 for use in the polymerization process. VAfter removal of the ethylene, the reactor eiiluent comprising solvent, dissolved polymer and catalyst is withdrawn from the llash chamber through line 2l and introduced into an intermediate portion of contacting tower 22.

Treatment of the polymer in contacting tower 22 takes place at a temperature at which the polymer is in solution. With ethylene polymers having molecular weight in the range of 20,000 to l50,000, temperatures between about 200 F. and about 400 F. can be advantageously employed. However, the solution temperature varies considerablywith ditlerent polyethylenes and may be as low as 180 P. Furthermore the solution temperature varies considerably with dillerent types of polymers and is not critical so long as the treatment takes place with the polymer in solution. When polymers of higher olens are being treated, the solution temperature may be considerably lower. A heat exchanger 23 is provided inline 21 in order to ensure that the polymer is in solution upon introduction into the contacting tower.

Contacting tower 22 can be any vessel suitable for contacting liquid materials in countercurrent flow. For example, it can be a vertical cylindrical pressure vessel which is properly insulated and designed to withstand elevated pressures. Line 24 connected to the lower portion of die contacting tower provides means for introducing a light hydrocarbon into the lower portion of the tower. Any suitable light hydrocarbon, preferably a paraliinic hydrocarbon containing from l to 6, and more desirably containing from 2 to 5, carbon atoms per molecule, and having, in general, a boiling point substantially lower, e. g., at least 25 F. lower, than the boiling point of the solvent employed in the polymerization reaction can be used. Examples of, but not exhaustive of, such lighthydrocarbons are ethane,ppropane, butane, isobutane, pentane, isopentane, hexane, isohexane, and the like.

The upper portion of contacting tower 22 is provided with a heating coil 25 through which a suitable heating fluid is circulated. Through the operation of the heating coil, the-upper portion of the tower is maintained at a temperature higher, e; g., 50 to 100 F. higher, than the lower portion of the tower. The temperature within the tower is generallyy inthe range ofnl50 to 500 F. dependingupon the particular polymer undergoing treatment. The pressure in the tower is such as to maintain the materials therein in the liquid phase` and will depend to a marked degree upon the light hydrocarbon used and the temperature in the tower. In general, `a large volume of light hydrocarbon, e. g., up to volumes of light hydrocarbon per volume of polymer solution, is employed in the contacting tower. The time of treatment can vary over a wide range, e. g., from 5 to 300 minutes, so long as there is adequate contact between the light hydrocarbon'and the polymer solution.

The light hydrocarbon, such as propane, introduced into the tower through line 24 contacts the polymer solution in countercurrent ow. During this contacting operation, the catalyst is caused to precipitate and settles inV the lower portion of the column. While it is not intended to limit the invention to any theory of operation, it is believed that addition of the light hydrocarbon in conjunction with the heating of the upper portion of the column causes a change in the solubility of the catalyst and polymer in the solvent and the light hydrocarbon. In other words, the addition of the light hydrocarbon reduces the solubility of the catalyst in the polymer solution, causing the catalyst to precipitate.

A polymer-rich phase is taken overhead from the contacting tower through line 26 and passed into flash charnher 27. ln flash chamber 27, a pressure is maintained somewhat lower than that in contacting tower 22., thereby causing the light hydrocarbon to be flashed off. The light hydrocarbon is removed from the liash chamber through line 2S and recycled to line 24 for subsequent use in the contacting tower. Polymer in solution in cyclohexane, which is recovered from the lower-portion of the flash chamber 27 through line 31, is'thenpassed into polymer recoveryzone 29. The polymer recoveryv zone can be any suitable means for recovering polymen from a solution thereof in a solvent and can comprise"r cooling and filtration equipment whereby the dissolved polymer is precipitated from solution by cooling Vand subsequently filtered. zone 29 through line 32 while polyethylene having alow ash content is withdrawn from the. zone through line 33u The cyclohexane removed from zone 29 can be recycled'v to line 12 for use in the polymerization reaction.

A catalyst-rich phase comprising propane, catalyst,.a`nd

polymer is withdrawn from the lower portion of contacting tower 22 through line 34. This catalyst-rich phasel is then passed into ash chamber 36 which is operated at a pressure lower than that maintained in contacting tower 22. The propane is tlashed overhead from flash chamber 36 through line 37 and then recycled to the contacting tower through line 24. The catalyst and polymer which is recovered from ash chamberk through line 38 may be recycled to line l2 for use in A portion of the usedi catalyst and polymer can be removed from the system,

the polymerization reaction.

as required by means of a line (not shown) connected to line 38, and then discarded or treated for recovery'.v of the polymer as desired. When using conventionaij processes as described hereinbefore to treat the polymer,

the catalyst is generally deactivated and thereby renderedl unsuitable for further use in the polymerization. However, the catalyst recovered in the instant process is not deactivated and can, therefore, be re-employed in the poly-, merization, thereby resulting in an improved productivity.,

The treating process of this invention is applicable to the polymers prepared by polymerization in the presenceA of a catalyst comprising a hydride or organo compound,"

e. g., a compound of a metal selected from the group consisting of aluminum, gallium, indium, and beryllium having the valence linkages thereof individually bound to organometal compound, including those where one or` more organo groups is replaced by a halogen, aV metal hydride, or a metal of groups l, Il, or lll, and the second' component is a group IV to Vl (Mendeleefs Periodic The organometal compounds referred to include, without limitation, ahryl, cycloalkyl, or aryl compoundsV of di,V

Cyclohexane is recovered from tri, tetravalent metals, particularly aluminum, gallium, indium, beryllium, sodium, potassium, lithium, rubidiurn, cesium, magnesium, cadmium, mercury, zinc, barium, lead, and tin, or such organometal compounds where one or more of the alkyl, cycloalkyl or aryl groups is replaced by a hydrogen atom and/ or a halogen atom. The organo groups can be quite large, compounds being applicable which have or more carbon atoms in each alkyl, cycloalkyl or aryl group and Ll0 or more carbon atoms in the molecule. Specic examples of such organometal compounds include triethylaluminum, triisobutylaluminum, a mixture of diethylaluminum chloride and ethylaluminum dichloride, sometimes referred to herein as ethylaluminum sesquichloride, diethylaluminum hydride, ethylaluminum dichloride, or diethylaluminum chloride, taken alone, trioctylalumintnn, tridodecylaluminum, triphenylaluminum, triphenylgallium, diphenylberyllium, dicyclohexylberyllium, cyclohexylzinc chloride, tetraphenyllead, tetraethyltin, and CHBAlCl, (C4H9)2A1Br, CBHNAHZ, (C3H7)2GaF, C6H11)2GaCl (cyclohexane derivative),

(Cslr) GHZ, CZgT/ LIGEQ (C1 4 29)2GaF (C6H5)2lnCl, CBHUnFZ, (CHuHnBrz (cyclohexane de rivative), ClHaBe, CHBBeBr, and the like.

The metal hydrides can include, as specic examples, aluminum hydride, lithium aluminum hydride, barium hydride, gallium hydride, indium hydride, sodium aluminum hydride, potassium beryllium hydride.

The metals of the iirst, second and third groups are applicable as a class, the most important members being sodium, magnesium and aluminum.

The compounds of a metal of group IV to VI or" the periodic system include the oxides, hydrides, halides, oxyhalides, and salts of organic acids, usually having twenty or less carbon atoms, such as formic acid, of the Group lV to VI metals such as titanium, zirconium, chromium, thorium, molybdenum and vanadium.

The alcoholates of a metal of group iV of the periodic system which can be employed conform to the formula XM(OR) where m-l-n equals the valence of the metal M, X is a halogen, and R is an organic radical usually having twenty or less carbon atoms, and preferably being an alkyl, cycloalkyl or aryl group. Specic examples of such alcoholates are titanium butoxide (termal-butyl titanate), tetra-sec-butyl titanate, tetraisopropyl titanate,

tetra-2-ethylbutyl titanate, tetra-2-ethylhexyl titanate, tetrastearyl titanate, tetraethyl titanate, tetra(chloroethyl) titanate, tetra-m-tolyl titanate, tetraallyl titanate, tetracyclohexenyl titanate, tetracyclopentyl titanate, tetraet'nyl Zirconate, tetramethyl zirconate, tetraisopropyl zirconate, l

tetraamyl zirconate, dichlorodiethyl titanate (CIZTKOCZHSM) monochlorotriethyl titanate (ClTi(OC2H5)3) and dichloro diethyl Zirconate (Cl2Zr(OC2H5)2) Also included are such compounds as H(OCH3)4, 'l`h(OC3H7)4,

A third catalyst component which can be used advantageously is an organic halide or metal halide where the organic radical has thirty or less carbon atoms, and is advantageously an alkyl, cycloalkyl or aryl group. Specie examples are ethyl bromide, ethyl trichloro titanium, l-bromobenzene, cyclohexyl chloride. Also applicable are an alkali metal or ammonium halide, an aluminum halide (where the catalyst also includes another metal compound such as a titanium compound), a halogen, a hydrogen halide, a complex hydride, a mixture of an organic halide and a metal, and Grignard reagent.

A still more specific subgroup of catalysts where excellent color and low ash content are obtained by the practice of the invention include catalysts in which an organornetal compound is used in combination with a metal salt. The ratios of the catalyst components can vary widely, depending upon the particular charge used and operating conditions, say from 0.02 to 50 mols of the iirst component per mol of the second catalyst component. If a third component is present, the amount can vary from 0.02 to 50 mols per mol of the second component.

Examples of suitable catalyst systems in accordance with the foregoing disclosure are as follows:

(a) Aluminum trialkyls, e. g., triethylaluminum or triisobutylaluminum and the tetravalent metal halides of the type represented by titanium tetrachloride;

(b) An organic halide (such as ethyl bromide), a group 1V inorganic halide (such as titanium tetrachloride), and a low valence metal selected from the group consisting of alkali metals, beryllium, magnesium, Zinc, cadmium, mercury, aluminum, gallium, indium, and thallium, for example, magnesium, ethyl bromide and titanium tetrachloride, as such, or with the addition of metallic aluminum;

(c) A group IV halide, for example, titanium tetrachloride, and a low valence metal identified in (b) for example, sodium or magnesium;

(d) A mixture of titanium hydride and an organometal compound exemplied by aluminum alkyl halide, i. e., a mixture of titanium hydride and ethylaluminum sesquichloride;

(e) Titanium dioxide and an organometal compound such as trialkylaluminum and aluminum alkyl chlorides, e. g., a mixture of titanium dioxide and ethylaluminum sesquichloride;

(f) A mixture of molybdenum pentachloride and organometal compounds and halides exemplified by tri ethylaluminum and ethylaluminum dichloride;

(g) A mixture of complex metal halides, exemplied by potassium uotitanate, and an organometal compound and halides exemplied by triethylaluminum and diethylaluminum chloride;

(h) A mixture of a derivative selected from the oxides of molybdenum, alkali metal and ammonium molybdates, and an organometal compound or halide exemplified by triisobutylaluminum and isobutylaluminum dichloride;

(i) A mixture of a derivative of iridium, platinum and osmium selected from the group consisting of halides, oxides and complex compounds of iridium, platinum and osmium, said complex compounds corresponding to the formula MIMXy, wherein M is an alkali metal or an ammonium radical, M is iridium, platinum or osmium, X is a halogen, and y at l 1 and the sum of :t and y is equal to the valence of M and a metallic organic compound exempliiied by triethylaluminum, for example, iridium chloride and triethylaluminum or ethylaluminum sesquichloride;

(j) At least one derivative selected from the group consisting of oxides, halides, and oxyhalides of vanadium and complex salts of said haiides with a member selected from the group consisting of ammonium halide and an alkali metal halide, and an organometal compound exemplied by triethylaluminum, for example, vanadium oxide and triethylalurninurn;

(k) A mixture of a derivative of a group Vl metal selected from the group consisting of halides, oxyhalides, hydroxyhalides, oxyhydroxyhalides of a metal selected from the group consisting of molybdenum, tungsten, uranium, selenium, tellurium, and polonium, and complex salts of said halides and said oxyhalides with a member selected from the group consisting of halides of sodium, potassium, lithium, rubidium, cesium and ammonia and an organometal compound exempliiied by triethylaluminum, for example, molybdenum pentachloride and ethylaluminum dichloride;

(l) A chromyl halide and at least one of the following (l) a metal hydride or an organometal compound, (2) an organometal halide, and (3) a mixture of an organic halide and a metal, for example, chromyl chloride, ethyl bromide and magnesium;

(m) 1) A titanium derivative, (2): a complex hydride- J (l) A hydrocarbon derivative of one of thermeti als,vzinc, cadmium, mercury, and magnesium and (2) a member selected from the group consisting of halides of titanium, zirconium, vanadium, and molybdenum, Voxyhalides of titanium, zirconium, vanadium, molybdenum and chromium, and complex salts of said halides and oxy halides with a member selected from the group consisting of halides of the alkali metals and ammonia, for example, diethylzinc and titanium tetrachloride;

(p) (l) An organo derivative of a group lV-A metal, (2) a hydride or -organo compound of a metal of groups. II to VH1, inclusive, and (3) a member selected from the group consisting of halogens and hydrogen halides, for example, triethylaluminum, titanium butoxide, and bromme;

(q) (l) A trior tetrahalide or titanium, zirconium, hafnium and germanium, (2) an `organophosphorus-containing compound, and (3) at least one of the following (a) an organometal halide, (b) a mixture of an organic halide and a metal and (c) a complex hydride, forexample, triethylaluminum, titanium tetrachloride and triphenyl phosphine; Y n

(r) (l) A trior tetrahalide of titanium, zirconium, hafnium, and germanium, (2) a peroxide of the formula ROOR' where R is hydrogen, alkyl, aralkyl, alkaryl, cycloalkyl, acyl, alkyne, or aryl and (3) at least one of the following: (a) an organometal halide (b) a mixture of an organic halide and a metal and (c) a complex hydride, for example, ethylaluminum sesquichloride, titanium tetrachloride and -benzoyl peroxide;

(s) (l) A trior tetrahalide of titanium, zirconium, hafnium and germanium, (2) a metal alkoxide, and (3) at least one of the following: (a) an organometal halide, (b) a mixture of an organic halide and a metal, and (c) a complex hydride; for. example, ethylaluminum sesquichloride, aluminum ethylate and titanium tetrachloride;

(t) (l) A halide of titanium, zirconium, hafnium, or germanium, (2) a hydride selected from the group consisting of hydrides of aluminum, gallium, indium and thallium and complexes of said hydrides with alkali metal hydrdes and (3) an organic halide; for example, titanium tetrachloride, lithium aluminum hydride and ethyl bro, mide;

(u) (l) A halide of titanium, zirconium, hafnium, or germanium, (2) carbides and acetylenic compounds, and (3) at least one of the following: (a) an organometal halide, (b) a mixture of an organic halide and a free metal, and (c) a complex hydride, for example, ethylaluminum sesquichloride, titanium tetrachloride, and copper acetylide.

The materials which are polymerized, in accordance with this invention, are polymerizable hydrocarbons, broadly. Preferably, the polymerizable hydrocarbons are olens containing a CH2=C radical. The preferred class of polymerizable hydrocarbons usedpis olens which are members of the ethylene series having up to and including eight carbon atoms per molecule. However, the polymerizable hydrocarbons used in the process of this invention also include diand polyoleiins in which the double `bonds are in non-conjugated positions.- Specifically, ethylene has been found to vpolymerize to a solid polymer immediately upon being contacted with-such catalyst` compositions. Examples of otherY polymerizable hydrocarbons which can be used in the process of this invention are propylene, l-butene, l-hexene, and1octene. vBranched chain olens can alsorbe used, suchas 8 l isobutylene,1 as well Aas 1,1-dialky1substituted:ethylenes; Examples of the diand polyolefins in which the double bonds areinv non-conjugated positions andtwhich can be used in accordance with this invention are 1,5-hexatriene, 1,4-pentadiene and 1,4,7-octatriene. Mixtures of` the foregoing polymerizable hydrocarbons can be polymerized to a solid polymer in the presence of the described catalysts, as, for example, by copolymerizing ethylene and propylene, ethylene and l-butene, propylene and 1-butene, or propylene and a pentene. Also arylV olens, e. `g., styrene and alkyl-substituted styrenes can be polymerized to a solid polymer in the process of this invention.

This invention is also applicable to the polymerization of a monomeric material comprising conjugated dienes containing from 4 to 8 or more carbon atoms. Examples of conjugated dienes which can be used include 1,3-butadiene, isoprene, 2,3'dimethylbutadiene, Z-methoxybuta` diene, Z-phenylbutadiene and the like.Y It isalso within the scope of the invention to polymerize such conjugated dienes either alone or in admixture with each other and/ or with one or more other compounds containing an active CH2= group which are copolymerizable therewith. Examples of such monoolens are listed above. Examples of other compounds containing the active CH2=C group include styrene, acrylonitrile, methyl acrylate, methyl methacrylate, vinyl chloride, Z-methyl- 5-vinylpyridine, 2-vinylpyridine,'etc.

Suitable solvents for use in the polymerization process are paraflns, cycloparaftins and/or aromatic hydrocarbons which are relatively inert, non-deleterious and liquid under the conditions of the process. The lower molecular weight alkanes, such as propane, butane, and pentane are especially useful when. the process is carried out at low temperatures. However, the higher molecular weight parai`n`ns and cycloparains, such as isooctane, cyclohexane, methylcyclohexane, and aromatic diluents, such as benzene, toluene, and the like, can also be used, particularly when operating at higher temperatures. When theprocess of the instant invention is used to treat the reaction mixture recovered from the polymerization process 'cli-` rectly, it is preferred that the solvent used in the process be one of the aforementioned higher molecular weight materials, e. g., -a hydrocarbon containing at least 6' Carn bon atoms per molecule. a v. A more comprehensive understanding of theinvention can be obtained by referring to the followingiillustrative example which is not intended, however, to be unduly limitative of the invention. v

EXAMPLE Ethylene was polymerized in the presence of a catalyst consisting of titanium tetrachloride and triisobutylaluminum. The reactor was initially charged with 2 liters of cyclohexane after treatment thereof with silica geland alumina in order to remove any moisturey- Thereafter, 1.94 grams of triisobutylaluminum and 0.56 gram of titanium tetrachloride were added to the reactor.. The reactor was flushed with nitrogen prior to and during the charging procedure to prevent contact ofthe reactant materials with air or moisture. The ethylene feed was passed through a purication system Vto remove oxygen, carbon dioxide and water prior to entering the reactor. The puriication system comprised an alkaline pyrogallol solution and a drying agent (silica-alumina). Ethylene was added to the reactor at a rate such as to maintain a pressure of about 300 p. s. i. g.v The temperature in the reactor during the polymerization was about 200 F. At the end of about three hours, the reaction mixture was heated to 250 F., blown into 4 liters of cyclohexane, and cooled overnight. n

A four percent polyethylene slurry in cyclohexane, prepared as described above, was treated in order to remove catalyst contained therein. The apparatus (bomb) used comprised a 17-inch long section of ll/z-inch stainless steel, capped pipe connected by a Iamesbury valve (a` full opening valve) to a 2-inch long capped section of the same type of pipe. About 202.1 grams of polyethylene slurry and 131 grams of butane were added to the bomb, constructed as described, thereby making a 39.1 weight percent butane in polymer-cyclohexane slurry. The bomb was then placed upright in an oven maintained at a temperature between 300 and 308 F. With the short section of pipe below the Jamesbury valve being in the down position. At the end of 11/2 hours, the Jamesbury valve was closed, the bomb cooled, and two separate slurry samples recovered, one from above and one from below the valve. These samples were placed in glass bombs with cc. of isopropyl alcohol and warmed with the bomb valves open to allow the butane to evaporate. The valves of the glass bombs were then closed, and the bombs were placed in an oven maintained at a temperature of about 180 F. for a period suicient for the polymer to enter solution. This procedure allowed the isopropyl alcohol to deactivate any catalyst contained in the solution. The bombs were then cooled, after which the polymer was removed for melt index and ash content determinations. The results of these tests are set forth hereinbelow in the table.

From the foregoing data, it is seen that by proceeding in accordance with the instant invention, a polymer product having a low ash content is obtained.

The polymers and copolymers produced in accordance with this invention have utility in applications where solid plastics are used. They are especially useful in applications requiring polymers of low ash content and polymers having a desirable white color which is retained even after the polymer is subjected to a molding operation. As will be evident to those skilled in the art, many variations and modifications ofthe invention can be made from a study of the foregoing disclosure. Such variations and modiiications are believed to be clearly within the spirit and scope of the invention.

I claim:

l. The process of treating a polymer prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of (l) a compound of a metal selected from the group consisting of aluminum, galliurn, indium, and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl, and aryl radicals, and (2) mixtures having at least two essential components, one of said components being a metal compound selected from the group consisting of group IV, group V and group Vl metal compounds, and another of said con ponents being selected from the group consisting of organometal compounds, metal hydrides, and metals of groups l, Il and Hl, which comprises contacting a sointion of said polymer in a hydrocarbon solvent, said solution containing said catalyst as an impurity, with a light paraiiinic hydrocarbon containing from l to 6, inclusive, carbon atoms per molecule and having a boiling point lower than that of Said hydrocarbon solvent; and separately recovering a polymer rich phase and a catalyst rich phase.

2. The process of claim 1 wherein said catalyst comprises triethylaluminum and titanium tetrachloride.

3. The process of claim 1 wherein said catalyst comprises triisobutylaluminum and titanium tetrachloride.

4. The process of claim l wherein said catalyst comprises ethylaluminum dichloride, diethylalurninum chloride and titanium tetrachloride.

5. The process of claim l wherein said catalyst com prises titanium tetrachloride, ethyl bromide and sodium.

6. The process of claim l wherein said catalyst comprises titanium tetrachloride and elemental aluminum.

7. The process of treating a polymer prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of (l) a compound of a metal selected from the group consisting of aluminium, gallium, indium, and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl, and aryl radicals, and (2) mixtures having at least two essential components, one of said components being a metal compound selected from the group consisting of group lV, group V and group VI metal compounds, and another of said components being selected from the group consisting of organometal compounds, metal hydrides, and metals of groups i, il and III which comprises countercurrently contacting a solution of said polymer in a hydrocarbon solvent, said solution containing said catalyst as an impurity, with a light paranic hydrocarbon containing from l to 6, inclusive, carbon atoms per molecule and having a lower boiling point than that of said hydrocarbon solvent; forming a polymer rich phase and a catalyst rich phase; and separately recovering said polymer rich phase and said catalyst rich phase.

S. The process of treating a polymer of ethylene, prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of l) a compound of a metal selected from the group consisting of aluminum, gallium, indium, and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl, and aryl radicals, and (2) mixtures having at least two essential components, one of said components being a metal compound selected from the group consisting of group IV, group V and group Vl metal compounds, and another of said components being selected from the group consisting of organo-metal compounds, metal hydrides, and metals of groups I, l1 and ill which comprises countercurrently contacting a solution of said polymer in a hydrocarbon solvent, said solution containing said catalyst as an impurity, with a light hydrocarbon having a lower boiling point than that of said hydrocarbon solvent, said contacting occurring at a temperature of at least F.; forming a polymer rich phase and a catalyst rich phase; and separately recovering said polymer rich phase and said catalyst rich phase.

9. The process of claim 8 wherein said light hydrocarbon has a boiling point at least about 25 F. lower than the boiling point of said hydrocarbon solvent.

l0. The process of claim 9 wherein said hydrocarbon solvent is cyclohexane and said light hydrocarbon is normal butane.

l1. The process of treating a polymer prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of (l) a compound of a metal selected from the group consisting of aluminum, gallium, indium, and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl, and aryl radicals, and (2) mixtures having at least two essential components, one oi said components being a metal compound selected from the group consisting of group IV, group V and group Vl metal compounds, and another of said components being selected from the group consisting of organometal compounds, metal hydrides, and metals oi groups l, il and ill which cornprises introducing a solution of said polymer in a hydrocarbon solvent, said solution containing said catalyst as an impurity, into an intermediate portion of an clon- HIl gated contacting zoneg'introducing a light paraftinic hydrocarbon containing from 1 to 6, inclusive carbon atoms per molecule and having a boiling point lower than that of said hydrocarbon solvent into a lower portion of said contacting zone; maintaining the upper portion of said contacting zone at a temperature higher than thatV within the lower portion of said zone; withdrawing a polymer rich phase from the upper portion of said contacting zone; and withdrawing a catalyst rich phase from the lower portion of said contacting zone.

12. The process of claim 11 wherein said polymer is polyethylene and the temperature within said contacting zone is at least 180 F.

13. A process for producing a polyethylene having a low ash content which comprises treating a solution of polyethylene in a hydrocarbon solvent with a light parafiinic hydrocarbon containing from 1 to"6, inclusive, carbon atoms per molecule and having a boiling point lower than that of said hydrocarbon solvent, said polyethylene having been prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of (1) a compound of a metal selected from the group consisting of aluminum, gallium, indium, and beryllium having the valence linkages thereof individually bound to members'selected from the group consisting of hydrogen, alkyl, cycloalkyl, and aryl radicals, and (2) mixtures having atleast two essential components, one of said components being a group IV to VI metal compound and another of said componentsbeing selected from the group consisting of organometal compounds, metal hydrides, and metals of groups I, II and III.

14. In a method for polymerizing polymerizable hydrocarbons comprising contacting in a reaction zone in the presence of a hydrocarbon solvent at least one polymerizable hydrocarbon with a catalyst having at least two essential components, one of said components being a metal compound selected from the group consisting of group IV, group V and group VI metal compounds, and another of said components being selected from the group consisting of organometal compounds, metal hydrides and metals of groups I, II and III, Yand recovering from said reaction zone a solution of polymer in said hydrocarbon solvents, said solution containing said catalyst as an impurity, the improvement which comprises contacting said recovered solution with alight hydrocarbon having a lower boiling point than that of said hydrocarbon solvent; forming a polymer rich phase and a catalyst rich phase comprising said light hydrocarbon,vsaid catalyst Vand polymer; separately recovering said polymer rich phase and said catalyst rich phase; separating said light hydrocarbon from said catalyst rich phase; and recycling said catalyst rich phase free of said light hydrocarbon to said reaction zone.

15. The process of treating .a polymerV prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of (l) a compound of a metal selected from the group consisting of aluminum, gallium, indium and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl radicals, and (2) mixtures obtained by mixing at least two essential components, one of said components being a metal compound selected from the group consisting of Igroup IV, group V, and group VIl metal com pounds, and another of said components being selected from the` group consisting of organometal compounds, metal hydrides, and metals of groups I, Il and III, which comprises contacting a solution ofV said polymer in a hydrocarbon solvent, said solution containing catalyst as an impurity with a light paraiiini-c hydrocarbon containing from 2 to 5, inclusive, carbon atoms per molecule and having a boiling point lower than that of said hydrocarbon solvent, the volume of said light paranic hydrocarbon used in said contacting being sulicient to form a separate phase'rich in catalyst, said contacting occurring at a temperature in Ythe range of to 500 F. and at a pressure suicient to maintain said light paranic hydrocarbon in the liquid phase; and separating a polymer rich phase from a catalyst rich phase. i

16. The process of treating a polymer prepared by catalytic polymerization in the presence of a catalyst se-y lected from the group consisting of (l) a compound of a metal selected from the group consisting of alu`- minum, gallium, indium and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyll and aryl radicals, and (2) mixtures obtained by mixing at least two essential components, one of said components being a metal compound selected from the group consisting of group IV, group V, and group VI metal compounds, and another of said components being selected from kthe group consisting of organometal compounds, metal hydrides, and metals of groups I, II and III, which comprises contacting a solution of said polymer in a hydrocarbon solvent, liquid at polymerization conditions 4and being selected from the group consisting of paraiiinic, cycloparanic and aromatic hydrocarbons containing at least 6 carbon atoms per molecule, said solution containing catalyst as an impurity, with a light paraiiinic hydrocarbon selected from the group consisting of propane and butanes, said light parainic hydrocarbon having a boiling point lower than that of said hydrocarbon solvent, the amount of said light paranic hydrocarbon used in said contacting being up to 10 volumes of light hydrocarbon per volume of polymer solution and suicient to form a separate phase rich in catalyst, said contacting occurring at a temperature in the range of 150 to 500 F. and at a pressure sufficient to maintain said light paratlinic hydrocarbon in the liquid phase; and separating a polymer rich phase from a catalyst rich phase. A

17. The process of treating a polymer prepared by' catalytic polymerization in the presence Vof a catalyst selected from the group consisting of (l) a compound of a metal selected fromy the group consisting of aluminum, gallium, indium and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl radicals, and (2) mixtures obtained by mixing 'at least two essential components, one of said components being a metal compound selected from theV group consisting of group IV, group V, and group VI metal'compounds, and another of said components being selected from the group consisting of organometal compounds, metal hydrides, and metals of groups I, II and III, which comprises countercurrently contactingin an Velongated contacting zone a solution of said polymer in a hydrocarbon solvent, liquid at polymerization conditions and being selected from the group vconsisting of paranic, cycloparanic and aromaticl hydrocarbons containing at least 6 carbon atoms per molecule, said solution containing catalyst as an impurity, with a light parainic hydrocarbon selected from the group consisting of propane and butanes, said light parainic hydrocarbon having a boiling point lower than that of said hydrocarbon solvent, the amount of, said light paratlinic hydrocarbon used in said contacting being up to 10 volumes of light hydrocarbon per volume of polymer solution and surcient to form a separate phase rich in catalyst, said contacting occurring at a temperature in the range of 150 to 500 F. and at a pressure sucient to maintain said light parafnic hydrocarbon in the liquid phase, and the upperportion of said contacting zone being maintained at a temperature from 50 to 100 F. higher than the lower portion of said zone; and separating a polymer rich phase from a catalyst rich phase. i

18. The process of treating-a polymer of ethylene prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of v(l) a compound of a metal selected from the group consisting of aluminum, gallium, indium and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl radicals, and (2) mixtures obtained by mixing at least tWo essential components, one of said components being a metal compound selected from the group consisting of group lV, group V, and group VI metal compounds, and .another of said components being selected from the group consisting of organometal compounds, metal hydrides, and metals of groups l, Il and III, which comprises contacting a solution of said polymer of ethylene in cyclohexane, said solution containing catalyst as an impurity, with butane, the amount of butane used in said contacting being up to 10 Volumes of butane per volume of polymer solution and sufficient to form a separate phase rich in catalyst, said contacting occurring at a temperature in the range of 150 to 500 F. and at a pressure suicient to maintain said butane in the liquid phase; and separating a polymer rich phase from a catalyst rich phase.

19. The process of treating a polymer of ethylene prepared by catalytic polymerization in the presence of a catalyst selected from the group consisting of (l) a compound of a metal selected from the group consisting of aluminum, gallium, indium and beryllium having the valence linkages thereof individually bound to members selected from the group consisting of hydrogen, alkyl, cycloalkyl and aryl radicals, `and (2) mixtures obtained by mixing at least two essential compounds, one of said components being a metal compound selected from the group consisting of group IV, group V, `and group VT metal compounds, land another of said components being selected from the group consisting of organometal compounds, metal hydrides, and metals of groups I, II and III, which comprises contacting a solution of said polymer of ethylene in cyclohexane, said solution containing catalyst as an impurity, with propane, the amount of propane used in said contacting being up to 10 volumes of propane per volume of polymer solution and sucient to form a separate phase rich in catalyst, said contacting occurring at a temperature in the range of to 500 F. and at a pressure suiicient to maintain said propane in the liquid phase; and separating a polymer rich phase from a catalyst rich phase.

20. A process of treating a polymer of ethylene prepared by catalytic polymezation in the presence of a catalyst obtained by mixing triisobutylaluminum and titanium tetrachloride which comprises contacting a solution of said polymer of ethylene in cyclohexane, said solution containing catalyst, with butane, the amount of butane used in said contacting being up to 10 volumes of butane per volume of polymer solution and suicient to form a separate phase rich in catalyst, said contacting occurring at a temperature in the range of 150 to 500 F. and at a pressure suflcient to maintain said butane in the liquid phase; and separating a polymer rich phase from a catalyst rich phase.

References Cited in the tile of this patent UNITED STATES PATENTS 2,405,547 Gaylor Oct. 5, 1948 2,691,008 Grim Oct. 5, 1954` 2,731,453 Field et al Ian. 17, 1956 FOREIGN PATENTS 874,215 Germany Apr. 20, 1953 538,782 Belgium Dec. 6, 1955 

1. THE PROCESS OF TREATING A POLYMER PREPARED BY CATALYTIC POLYMERIZATION IN THE PRESENCE OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF (1) A COMPOUND OF A METAL SELECTED FROM THE GROUP CONSISTING OF ALUMINUM, GALLIUM, INDIUM, AND BERYLLIUM HAVING THE VALENCE LINKAGES THEREOF INDIVIDUALLY BOUND TO MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL, CYCLOALKYL, AND ARYL RADICALS, AND (2) MIXTURES HAVING AT LEAST TWO ESSENTIAL COMPONENTS, ONE OF SAID COMPONENTS BEING A METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF GROUP IV, GROUP V AND GROUP VI METAL COMPOUNDS, AND ANOTHER OF SAID COMPONENTS BEING SELECTED FROM THE GROUP CONSISTING OF ORGANOMETAL COMPOUNDS, METAL HYDRIDES, AND METALS OF 